Triazine containing azo dyestuffs



United States Patent 3,454,551 TRIAZINE CONTAINING AZO DYESTUFFS Angelo Mangini, Germana Mazzanti, and Antonio Tundo, Bologna, Italy, assignors to Aziende Colori Nazionali Allini ACNA S.p.A., Milan, Italy N0 Drawing. Filed June 1, 1964, Ser. No. 371,786 Claims priority, application Italy, June 5, 1963, 11,724/ 63 Int. Cl. C091) 62/44, 62/82 US. Cl. 260-153 Claims ABSTRACT OF THE DISCLOSURE Dyestuffs containing the reactive radical:

wherein R is a hydrocarbon radical, benzene nucleus, or a substituted benzene nucleus.

Our invention relates to a new class of reactive dyestuffs, and more particularly to dyestuffs capable of forming, during dyeing, chemical bonds with the hydroxyl groups of cellulose, thereby yielding dyeing particularly fast to the wet treatments.

Our new class of dyestuffs contains the reactive radical A IXIWINI wherein R is a hydrocarbon radical, benzene nucleus, or a substituted benzene nucleus.

The dyestuffs of our invention are prepared by reacting cyanuric chloride with a compound containing 2 alcoholic or phenolic hydroxyl groups and then condensing the product (II) obtained with variously substituted aromatic diamines, according to the reactions:

wherein Ar is selected from the group consisting of substituted benzene, naphthalene, and diphenyl nucleus and R has the above defined meaning. By diazotation of the 3,454,551 Patented July 8,1969

amine (III) and coupling with different coupling agents, reactive dyestuffs having the structure (IV):

wherein Ar and R have the above-defined meaning and R is a residue of sulphonated pyrazolone derivatives, sulphonated naphthylamines, sulphonated naphthols, sulphonated amino-naphthols, etc. are obtained.

The reactive dyestuffs of our invention can alternatively be prepared by condensing the derivative (H) with differently substituted amino-naphthols according to the reaction:

soaNa OH I NaO S 2 then coupling the naphthol (V) with different diazonium salts to yield reactive dyestuffs (VI):

NaO S VI) wherein Ar is a differently substituted benzene, naphthalene or diphenyl nucleus and R has the above defined meaning.

The derivative (II) can, by another alternative, be directly condensed with the azo dyestuffs, with Cuphthalocyanine dyestuffs or with sulphonated anthraquinone dyestulfs, containing a free amino group to yield directly the reactive dyestuffs (VII):

EXAMPLE 1 Preparation of the amine 0.2 mol of collidine and 0.1 mol of ethylene glycol, dissolved in cc. acetone, Were added to a solution of 0.2

mol of cyanurie chloride in 280 cc. acetone. The cyanuric chloride was cooled with ice and the addition of collidine and ethylene glycol was at a rate so as to maintain the reaction mixture at about C. At the termination of the addition, the whole was boiled for 12 hours on a water bath. After cooling, the hydrochloride was separated from the collidine by filtration.

The acetone solution was then poured, under agitation, into 500 grams of crushed ice. The condensation product between the ethylene glycol and the cyanuric chloride was thus prepared; this condensation product, when crystallized from ligroin, melts at 142143 C.

0.01 mol of the condensation product between ethylene glycol and the cyanuric chloride was dissolved in 35 cc. acetone and the solution was poured into water and ice (40 parts of ice and 40 cc. H O). The neutral solution of 0.02 mol of sulphonated m-phenylendiamine in 120 cc. of Water containing 0.02 mol of sodium acetate was added, under vigorous agitation, to the suspension obtained. The whole was agitated for 4 hours at 4045 C. to give a diamine having the structure:

or or 4 EXAMPLE 2 By proceeding as in Example 1, but using as the coupling agent 1-(2',5'-dichloro-4-sulpho)-phenyl-3-methyl- 5-pyrazolone, a dyestufi of the structure:

which dyes cotton a fast brilliant yellow shade, was obtained.

EXAMPLE 3 Preparation of the dyestutf To the aqueous solution of the amine obtained above was added 0.09 mol of concentrate HCl diluted with 10 cc. of water. This was diazotized with 0.02 mol of NaNO; at 510 C. After removal of excess NaNO the diazoni um salt was added under agitation to the alkaline solution (Ph of 8) of 0.02 mol of K-benzoyl acid in 50 cc. of water. During addition of the diazonium salt, the temperature of the solution containing the coupling agent was kept between 4 and 6 C. and the pH was maintained between 8 and 8.5 by suitable additions of 10% NaOH. The reaction mass was agitated for 4-5 hours after which the pH was brought to 7.3. The mass was salted with NaCl and the precipitate, collected by centrifuging, was dried at C.

The dyestuff thus obtained had the structure;

and dyed cotton a fast red shade.

the suspension obtained. The reaction mass was agitated for 10 hours at 40-45 C. A solution containing the condensation product with the structure:

was obtained.

0.02 mol of m-amino-benzoic acid was diazotized at 5-6 C. and the diazonium salt was poured dropwise in the solution neutralized With 10% Na CO (pH of 8) of the condensation product obtained as described above. During the diazoniu-m salt addition, the temperature of the solution of the coupling agent was maintained between 4 and 6 C. and the pH between 8 and 8.5 by suitable additions of 10% NaOH. The reaction mass was agitated for 4-5 hours and the pH was then brought to 7.3. The mass was salted with NaCl and the precipitate, collected by centrifuging was dried at 40 C. The dyestutf obtained has the structure:

and dyes cotton an orange shade fast to wet treatments.

5 6 EXAMPLE 4 dyes cotton a red shade fast to laundering and has the By proceeding as described in the preceding example structum: but using the diazonium salt of the Tobias acid as coupling agent, the dyestutf: 1 OH SOaNa H 01 N=N \Na0aSNHkN/LO moss NHL N "OCHa- 2 SOaNa SOsN which dyes cotton an orange shade fast to wet treatments, OC NH 0H E was obtained. l l I EXAMPLE 5 N N N N By proceeding as described in Examples 3 and 4, but using the diazonium salt of the 1-amino-4-acetylamino-2- \NaOaS- NH- 0 sulpho-benzene as the dyestuif with coupling agent, the 303m N structure: some SO Na (IE ([31 CHv-CO-NH--N=N:@O

N O NH- O-CH a 38 \N i- 2 which dyes cotton a scarlet shade fast to wet treatments, was obtained. XA E EXAMPLE 7 E MPL 6 h 11 0.2 mol of collidme and 0.1 mol of resorcln, dlssolved T e f0 owmg dyestufi in 200 cc. acetone were added by cooling in ice to a solution of 0.2 mol of cyanuric chloride in 280 cc. acetone at a rate so as to maintain the reaction mixture at about 10 C. At the end of the collidine and resorcin addition, OH the mass was agitated for 5 hours at 20 and then for 2 hours at 50-55 C. The whole was cooled and the colli- 35 N=N N dine hydrochloride was filtered ofl. =O0H4 The acetone solution was then poured, under agitation HN Naaso' N into 500 g. of crushed ice. A yellow-orange product was 0 some separated; it was crystallized with ligroin (MP. 141- B 2 143 C.) and has the following structure: 40

i F N N N N was obtained by proceeding as in Example 6, but using L J IL J the N-acetyl-isogamma acid as the coupling agent. It dyes cotton an orange brown shade fast to laundering. 0.01 mol of this product was dissolved in 40 cc. ace- EXAMPLE 8 tone and the solution was poured in water and ice cc. water and 50 g. ice). The neutral solution of 0.02 mol of sulphonated m-phenylendiarnine and 0.02 mol of sodium 50 acetate in 100 Water was added under vigorous agita m 40 cc. acetone and the solution was poured in water and tion to the suspension thus obtained. The mass was agiice Water and 50 A Solution f 002 mol of t t d f 4 hours t 40.45" C, A aqueous l ti of isogamma acid and 0.02 mol of sodium acetate in 100 cc. the following product: Water was added under vigorous agitation to the suspen- 0.01 mol of the previously described condensation product between cyanuric chloride and resorcin was dissolved (31 31 am A 1 1m NaOaS-NH-kNJ0- O-k -NHQ'SmNa was obtained which, after neutralization with 10% sodision thus obtained. The whole was agitated for 7 hours at um carbonate, and the addition of 0.09 mol of concen- 40-45 C.-A sol-utlon of: trate HCl diluted with 10 cc. water, was diazotized at 5- 0 01 11 10 C. with 0.02 mol of sodium nitrite. After removal of the NaNO excess, the diazonium salt was added under agitation to the alkaline solution (pl-i=8) of 0.03 mol of K-benzoyl acid in 60 cc. water. During the addition of Naoas the diazonium salt, the temperature of the solution containing the coupling agent was maintained between 4 and 7 OH C1 6 C. and the pH between 8 and 8.5 by suitable addition I of 10% NaOH. The reaction mass was kept under agitation for 4-5 hours and then the pH was adjusted to 7.3. The mass was salted with NaCl and the precipitate col- NaO S lected by centrifuging was dried at 40 C. The dyestuif ([1 l N N W Ito I! l N S O Na 3. A reactive dyestuif of the formula:

We claim: 1. A dyestufi of the formula:

CGHOCHI|\T CoII5-OCHN 2 A reactive dyestuif of the formula:

H3CT'J C N:N N

S OgNfl H3C-C -C N=N 0.02 mol of sulphonated p-aminoacetoanilide in 15 cc. water was added at 5 C. to 0.09 mol of HCl diluted with 10 cc. water. The whole was diazotized between 5 and 8 C. with a solution of 0.02 mol of NaNO in 10 cc. water. The suspension of the diazonium salt was added to the (|)l;[ SO5Na or: 5-@- 8) of the product obtained as described above. During addition of diazonium salt, the

was obtained which, after neutralization with 10% Na CO Was used for the preparation of the dyestuff:

l soaNa l SOaNa NH SO Na alkaline solution (pH:

temperature of the solution containing the coupling agent was maintained between 4 and 6 C. and the pH between 8 and 8.5 by suitable additions of 10% NaOH. The reaction mass was agitated for 4-5 hours and then the pH was brought to 7.3. The reaction mass was salted wit NaCl and the precipitate, collected by centrifuging, was dried at C. The dyestuff dyes cotton a scarlet shade fast to washing.

EXAMPLE 9 The dyestuff:

S OaNa SIOaNa NaO;S

O O O H NaOaS NaOaS 4. A reactive dyestulf of the formula:

sO3Na NaOaS was obtained similarly to Example 8, using o-amino-ben- 50 zene-sulphonic acid as the diazonium salt. It dyes cotton a brilliant orange shade possessing excellent fastness to washing.

EXAMPLE 10 The dyestuif:

was obtained by proceeding as in Example 8 but using the diazonium salt of Tobias acid, and dyes cotton an orange shade possessing excellent fastness to wet treatments, such as washing. 

